ISSN 10619348, Journal of Analytical Chemistry, 2012, Vol. 67, No. 6, pp. 550554. Pleiades Publishing, Ltd., 2012.

Original Russian Text G.I. Marinina, M.S. Vasilyeva, A.S. Lapina, 2012, published in Zhurnal Analiticheskoi Khimii, 2012, Vol. 67, No. 6, pp. 608612.

ARTICLES

Behavior of a RutheniumTitanium Oxide Film Electrode (RTOE)

in Potentiometry
G. I. Marinina, M. S. Vasilyeva, and A. S. Lapina
Far Eastern Federal University, Sukhanova st. 8, Vladivostok, 690950 Russia
Email: mgalina_7@mail.ru
Received October 13, 2010; in final form November 9, 2011

AbstractPolyfunctional properties of a rutheniumtitanium oxide electrode in the absence of polarization

and the possibility of its application to the potentiometric detection of iron(III) titration with an ethylenedi
aminetetraacetic acid solution, acidbase and redox reaction types have been demonstrated. Mechanisms of
reactions determining the potentials of electrodes of this type have been investigated by a number of methods.
Keywords: rutheniumtitanium oxide electrode, potentiometry.
DOI: 10.1134/S1061934812060081

Recently, the creation of new metal oxide, in par

ticular, metal oxide film electrodes (MOFE) and com
prehensive studies of the available ones has offered a
promising direction in the development of electroana
lyical sensors because of the low cost of the new elec
trodes as compared to noblemetal electrodes, and
easiness of work with them.
The rutheniumtitanium oxide anode (RTOA)
characterized by high corrosion stability, the stability
of electrochemical parameters within long operation
times, and high selectivity provides an example of
MOFE. RTOA is extensively used in applied electro
chemistry, first of all, in chlorine and sodium hydrox
ide production, in the synthesis of sodium hypochlo
rite by the electrochemical method, seawater electrol
ysis, etc. [15]. At present, RTOAs, including those
modified by different elements, are used as sensors in
different methods of electrochemical analysis [68].
It was demonstrated in [6] that the RuO2Ti electrode
is a highly sensitive and easytooperate sensor for
pH detection, with the slope of the pHfunction
56.03 mV/pH and, simultaneously, insensitive to the
presence of Li+, Na+, and Ca2+ ions.
A NiRuO2 electrode was used as an indicator
electrode for the voltammetric determination of
ethanol [8] and the evaluation of the acid number of
oils [7].
Ni/P composites on titanium(IV) oxide with nano
additives of RuO2 [9] were used for the amperometric
determination of ethanol in 0.2 M NaOH.
Electrodes comprising film coatings on a titanium
substrate with different amounts of Ti(IV), Ru(IV),
and Sb(III) oxides were investigated [10], and their
linear dependence with a higher slope ratio as
compared to the theoretical one was demonstrated.

In the present work, the behavior of RTOA in the

absence of polarization and in potentiometric titration
by different reaction types was studied. In the revela
tion of the indicator properties, the mechanism of the
reaction determining the electrode potential was
investigated by a number of methods (constructing
kinetic, concentration, and voltamperometric curves).
EXPERIMENTAL
The MOFE consisted of titanium plates of the VT
10 grade (2.5 0.5 0.1 cm3) with a deposited active
layer of titanium and ruthenium oxides in the ratio
30 : 70 mol %.
Prior to depositing the active layer, titanium plates
were kept for 5 min in hot conc. HCl, then for 20 min
in a saturated 224 solution, and then washed in
distilled water. The active layer was deposited on the
thus prepared titanium plates by the thermal decom
position of a mixture of ruthenium hydroxochloride
and titanium chloride according to [11].
Potentiometric measurements were carried out on
a portable Radelkis OP265/1 ion and pHmeter.
The Radelkis OP0830P calomel electrode served
as a reference electrode. An automated Radelkis
930/1 burette was used for titration measure
ments.
Voltammograms were recorded on a Radelkis
105 polarograph. A twoelectrode cell consisting
of a working electrode and a silversilver chloride ref
erence electrode was used. The potential sweep rate
was 0.01 V/s.

550

BEHAVIOR OF A RUTHENIUMTITANIUM OXIDE FILM ELECTRODE

E, mV

551

E, mV
1
2

600

400

150

50

1
2

200
200

400

t, sec

3
4
4
5
6

50

pc

Fig. 2. Epc dependence for (1) RTOA/Fe(III);

(2) RTOA/EDTA; (3) Pt/EDTA; (4) Pt/Fe(III).

Fig. 1. Kinetic curves of RTOA in the potentiometric titra

tion of 0.05 M Fe(III) with 0.1 M EDTA. V (EDTA), mL:
10; 24; 35; 46; 58; 610.

an analytical signal as the potential jump in the poten

tiometric titration of Fe(III) using RTOA.

RESULTS AND DISCUSSION

Potentiometric complexometric titration. The poten
tiometric titration of a component of the reversible
redox system Fe(III)/Fe(II) was performed with
EDTA using RTOA as an indicator electrode. A Pt
electrode was used as a reference electrode.
The potential jump values depending on the used
dilution of solutions are shown in Table 1. At low con
centrations, the potential jumps on Pt and RTOA elec
trodes are comparable to each other and increase with
concentrations for both of them. As the concentration
of the iron(III) solution increases, for RTOA one
observes a more dramatic potential change in the titra
tion endpoint than for Pt, which offers an advantage
of an indicator electrode in its application in potenti
ometric titration.
The stability of the RTOA potential over time was
studied in the titration of a 0.05 M iron(III) solution
with a 0.1 M EDTA solution by measuring the elec
trode potential to the constant value upon the addition
of each next titrant portion (Fig. 1). Prior to titration,
10 mL of an iron(III) solution was mixed with 2 mL of
a 25% solution of ammonium acetate, 1 mL of a
0.05 M solution of Mohrs salt, and 20 mL of distilled
water. As it was found, the quasistationary value of the
RTOA potential established within ~5 min.
The values of quasistationary electrode potentials
in 0.1 M solutions of Fe(III) and complexone III mea
sured using an RTOA and a Pt electrode are presented
in Table 2. As follows from this Table, RTOA exhibits
higher potential in the solutions under study than the
Ptelectrode, which is indicative of the effect of the
electrode material on the potential value. The differ
ence in the potential values of the titrate and titrant is
~250 mV, which allows us to suppose the emergence of
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In all cases, the dependences of potentials on the

titrate and titrant concentrations in potentiometric
complexometric titration (Epc) were characterized
by correlation coefficients close to unity (Table 3),
indicating the high degree of linearity. One can observe
three main types of the Epc dependence (Fig. 2):
(1) dependence close to the Nernstian one in the pc
range 14 with the slope ~71 mV for the case of
iron(III) on RTOA (curve 1); (2) curves with slopes
substantially higher than the Nernstian one
(~162 mV) in the pc range 13 in the case of iron(III)
on a Ptelectrode (curve 4); and (3) RTOA and
Ptelectrode potentials independent of the complex
one III potential (curves 2, 3). The higher slopes of the
concentration dependence are characteristic for metal
oxide electrodes, which can be related to differences in
the stoichiometric compositions of oxides of the met
als under study, their semiconductor properties,
method of fabrication, surface conditions, etc.
[12, 13].
Table 1. Potential jumps for RTOA and Ptelectrode in the
titration of a Fe(III) solution with an EDTA solution (n = 10;
P = 0.95)
c, M

Potential jump dE/dV, mV/mL

Fe(III)

EDTA

Pt

RTOA

0.025
0.025
0.05
0.05
0.1

0.025
0.05
0.05
0.1
0.1

93.33 6.76
143.33 5.70
190.00 7.83
243.67 2.61
866.67 16.40

136.67 2.85
220.00 9.34
320.00 3.11
516.67 5.68
1660.00 2.14

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MARININA et al.

Table 2. Quasistationary values of electrode potentials in

0.1 M solutions of Fe(II) and EDTA (n = 10; P = 0.95)
Potential (mV) in solutions
Electrode
Pt
RTOA

Fe(III)

EDTA

501 4
565 3

124 3
318 2

Table 3. Results of regression analysis for a Fe(III) solution

in the cases of the Ptelectrode and RTOA (n = 3; P = 0.95)
Electrode
Pt

Concentration
range

R2

101105

E = 594.3 110.4 pc

0.91

1104

E = 773.9 133.5 pc

0.93

10

10 10
RTOA

Regression
equations

E = 1013.0 162.3 pc

0.93

10

1105

E = 603.0 53.8 pc

0.90

10

1104

E = 708.2 70.9 pc

0.99

Studies of RTOA behavior in potentiometric pH mea

surement. The RTOA behavior in direct pH measure
ments and acidbase titration was studied in compar
ison to a glass electrode (GE) at pH 2.0912.00. The
linear Epc dependence for RTOA, just as for GE, was
observed over the whole pH range (Fig. 3). For GE,
the slope of the Epc dependence was (57.25
1.53) mV/pH (correlation coefficient R = 0.99). The
slope of the Epc dependence was (56.76
2.17) mV/pH, R = 0.98 (Table 4). Thus, the linearity
of the RTOA pHfunction in a broad pH range was
demonstrated in agreement with the literature data
[7].
The potentiometric titration of 0.1 M H2SO4 with a
0.1 M solution of NaOH was carried out using a GE, a
Ptelectrode, and an RTOA as indicator electrodes
(Fig. 4).
E, mV

As was expected, the highest potential jump was

obtained for GE (Fig. 4, curve 1). For RTOA, the
potential jump was comparable with that for GE, suf
ficiently large and stable over time (Fig. 4, curve 2). An
electrode based on RuO2 was used in the titration of
0.05 M H3PO4 with a 0.1 M solution of NaOH; the
results were well reproducible within long operation
[7]. In the titration with a Ptelectrode the potential
established rapidly, but the value of the analytical sig
nal was not high (Fig. 4, curve 3); the very fact of signal
presence confirms the similarity of the behavior of Pt
electrode with that of typical metaloxide electrodes in
pH measurements [1].
A substantial disadvantage of the glass electrode
consists in its high resistance, fragility, the necessity of
its pretreatment and soaking in solution of the ion to
be determined. The only factor of the deterioration of
RTOA properties can be related to the electrode
scratching by solid equipment, such as the sharp edges
of tools [7].
RTOA application to potentiometric redox titration
was studied on an example of titration of the compo
nent of the reversible Fe(II) system by those of the
irreversible Cr(VI) and reversible Ce(IV) systems.
As can be seen in Table 4, the signal on the Ptelec
trode in the titration of Fe(II) with a solution of Cr(VI)
is substantially lower than those for two reversible sys
tems. A similar dependence was observed for RTOA as
well. For irreversible systems, the rate constant of the
redox process and the exchange current are lower than
those for the reversible one. To increase E/V, polar
ized electrodes should be used. This problem does not
arise for a reversible system.
For the Ptelectrode and RTOA, the titration
curves are of the integral type characteristic for poten
E, mV
500

300

100

400
200

100
2

10

3
V, mL
4

pH

200

300

Fig. 3. Dependence of potential E on the pH of solution:

(1) RTOA; (2) GE.

Fig. 4. Potentiometric titration curves of 0.1 M H2SO4

with a 0.1 M NaOH solution using (1) GE; (2) RTOA, and
(3) Pt.

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BEHAVIOR OF A RUTHENIUMTITANIUM OXIDE FILM ELECTRODE

553

Table 4. Results of mathematical processing of analytical signals of the Ptelectrode and RTOA in potentiometric redox
titration (n = 3; P = 0.95)
Electrode
Pt
RTOA

Systems under study

Fe(II)/Ce(IV)
Fe(II)/Cr(VI)
Fe(II)/Ce(IV)
Fe(II)/Cr(VI)

dE/dV, mL
2033
713
1300
390

tiometric titration: a large and dramatic potential

jump is observed in the equivalence point. In the case
of participation of an irreversible electrochemical sys
tem in the titration process, RTOA is characterized by
lower dispersion values as compared to the Ptelec
trode, which points to the better reproducibility of the
results for the former one (Table 4).
To more comprehensively characterize the elec
trode process, quasistationary polarization curves
were recorded in solutions of reversible electrochemi
cal systems. For comparison we used the wellknown

9.00
12.00
15.81
8.37

The polarization curves are of the classical type.

The analysis of the curves on the Tafel equation coor
dinates (Fig. 5) enabled us to estimate the exchange
current: for the [Fe(CN)6]3+/[Fe(CN)6]4+ system on
the Ptelectrode it was 106 A/cm2 and for the
Fe3+/Fe2+ system, 107. For RTOA, the exchange
currents were equal to ~105 A/cm2 for the

1.5

1.0

1.0

0.5

0.5

0.5

5.5
logi 0.5

1.0

1.0

(b)

6.5

(c)

E, V

2
9
9
1

ideally reversible system [Fe(CN)6]3+/[Fe(CN)6]4+ in a

neutral medium (1 M Na2SO4) and the reversible sys
tem Fe3+/Fe2+ in an acidic medium (1 M 2SO4).

1.5

6.5

tS/ n

81.00
144.00
249.95
70.05

E, V

()

E, V

S2

6.0

5.5
logi

(d)
E, V
0.5

1.0
0.5
5.5
0.5

5.5

4.5
logi

5.0
logi

0.5
1.0
1.0

1.5

Fig. 5. Quasistationary polarization curves for (a, b) Pt and (c, d) RTOA in (a, c) [Fe(CN)6]3/[Fe(CN)6]4 and
(b, d) Fe3+/Fe2+ electrochemical systems.
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MARININA et al.

[Fe(CN)6]3+/[Fe(CN)6]4+ system and ~106 A/cm2 for

the Fe3+/Fe2+ system. Exchange current is an impor
tant kinetic characteristic of the stage of charge trans
fer, indicative of the degree of reversibility of an elec
trochemical reaction and characteristic of the rate of
exchange of charged particles between the electrode
and the electrolyte at the equilibrium potential. For
RTOA exchange currents and, therefore, the degree of
reversibility of an electrochemical process were higher
than those of the Ptelectrode. This is in agreement
with the earlier obtained data for potentiometric titra
tion of iron(III) with an EDTA solution using RTOA
as an indicator electrode.
A certain difference in the values of exchange cur
rents in the reversible electrochemical systems can be
explained by the effect of medium acidity. In an acidic
medium (for the Fe3+/Fe2+ system), the exchange cur
rents for both platinum electrode and RTOA are one
order of magnitude higher, which is indicative of the
effect of hydrogen ions on the establishment of the
electrode equilibrium.

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ACKNOWLEDGEMENTS
The authors are grateful to E.V. Shchitovskaya for
her help in sample preparation and studies.

11. Kondrikov, N.B., Shchitovskaya, E.V., Vasileva, M.S.,

Kuryavyi, V.G., Rudnev, V.S., Tyrina, L.M., and Gor
dienko, P.S. http://zhurnal.ape.relarn.ru/articles/
2002/092.pdf

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